Abstract

The cationic ruthenium allenylidene complex RRuRax−[Ru(indenyl)L(PPh3)CCCPh2]+PF6 catalyzes the etherification of secondary and tertiary propargylic alcohols in a formal nucleophilic substitution reaction utilizing primary and secondary alcohols as the nucleophiles. At a catalyst loading of only 1.1mol%, the corresponding propargylic ether products were obtained in 9 to 73% isolated yields (18h reaction time at 100°C); no further additives are required. The reaction exhibits an induction period; as shown by a control reaction, the high reaction temperature may chemically change the allenylidene complex to be employed as the catalyst but does not lead to catalyst deactivation.

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